Novel oximecarbamates

ABSTRACT

New compounds of the formula: WHEREIN R1 is either lower-alkylthio, ar(lower-alkyl)thio, arylthio or lower-alkenylthio; R2 is R1 or chloro; and R3 is lower-alkyl. The compounds are useful as nematocides, insecticides and acaricides. This application is a divisional of co-pending Application Ser. No. 701,572, filed Jan. 30, 1968 now U.S. Pat. No. 3,632,621.

, United States Patent Addor et al.

[54] NOVEL OXIMECARBAMATES [72] Inventors: Roger Williams Addor, Pennington;

Frank Albert Wagner, .ll'., Hopewell, both of NJ.

[73] Assigneez American 'Cyanamld Company,

Stamford, Conn.

[22] Filed: -March8, 1971 [21] Appl.No.: 122,197

Related US. Application Data [62] Division of Ser. No. 701,572, Jan. 30, 1968,

Pat. No. 3,632,621.

52 us. Cl. ..260/4S3 R 511 rm. 0].; ..C07C 119/00 [58] Field 6: Search ..260/453 R, 566 AC [56] References Cited UNITED STATES PATENTS 3,506,698 '4/|970 Jelinek 260/4531! [451 Sept. 26, 1972 Buchanan ..260/453 R Fridinger et al....260/453 R X Primary Examiner-Leon Zitver Assistant Examiner-Gerald A. Schwartz Attorney-Robert P. Raymond [57] ABSTRACT New compounds of the formula:

ful as nematocides, insecticides and acaricides.

4 Claims, No Drawings NOVEL OXIMECARBAMATES This application is a divisional of co-pending Application Ser. No. 701,572, filed Jan. 30, 1968 now US. Pat. No. 3,632,621.

This invention relates to and'has for its object the provision of new oxime carbamates. It relates further to the provision of pesticidal compositions containing said newoxime carbamates and, still further, to the use of these compositions as insecticides, acaricides and nematocides.

The compounds according to this invention are represented by the following formula (I):

wherein R is either lower-alkylthio, ar(lower-alkyl)thio, arylthio or lower-alkenylthio; R is R or chloro; andR is lower-alkyl.

The term lower-alkyl" includes straight, branched and cyclic saturated hydrocarbon radicals having up to seven carbons, as exemplified by methyl, ethyl, npropyl, n-butyl, sec-butyl, amyl, sec.-amyl, n-hexyl, cyclohexyl and n-heptyl.

The term ar(lower-alkyl) includes monocyclic and bicyclic radicals having from one to six carbon atoms in the alkyl radical. The aryl radicals may be phenyl or naphthyl or lower-alkyl substituted analogues thereof. Preferred ar(lower-alkyl) are benzyl and phenethyl radicals.

The term aryl includes such aryl moieties as were described in the preceding paragraph.

The term lower-alkenyl includes alkenyl radicals of one to seven carbon atoms as for example allyl and methallyl as well as alkenyl radicals having an aryl substituent, e.g. styryl or cinnamyl.

Among the compounds which are included in the scope of Formula I are:

O-(m'ethylcarbamoyl) methylthiochloroformaldehyde oxime O-(propylcarbamoyl) butylthiochlorofonnaldehyde oxime O-(ethylcarbamoyl) butylthiochloroformaldehyde oxime O-(propylcarbamoyl) benzylthiochloroformaldehyde oxime O-(ethylcarbamoyl) phenylthiochloroformaldehyde oxime O-(methylcarbamoyl) allylthiochloroformaldehyde oxime O-(butylcarbamoyl) methallylthiochloroformaldehyde oxime O-(methylcarbamoyl) bis-methylthioformaldehyde oxime o-(propylcarbamoyl) bis-butylthioformaldehyde oxime O-(methylcarbamoyl) (methylthio)ethylthioformaldehyde oxime O-(ethylcarbamoyl) (methylthio)butylthioformaldehyde oxime O-(methylcarbamoyl) bis-benzylthioformaldehyde oxime O-(ethylcarbamoyl) bis-phenylthioformaldehyde oxime 2 O-(butylcarbamoyl) bis-allylthioformaldehyde oxime O-(ethylcarbamoyl) bis-methallylthioformaldehyde oxime The compounds of this invention are prepared by reacting at least one mole of a carbamate of dichloroformaldehyde oxime represented by the formula (II):

with one mole of a mercaptan of the formula (III):

wherein R and R are as defined above. When the oxime is reacted with only one mole of mercaptan, the product which is obtained is that of Formula I wherein R is chloro. When two moles of mercaptan are reacted, the compounds of Formula I wherein R is not chloro, are obtained. When the oxime is reacted with two moles of mercaptan, it is possible to employ one mole each of different mercaptans. In this case, the mercaptans can be reacted either concurrently or sequentially.

Preferably, the reaction is carried out in the presence of a base at a temperature ranging from minus 50 to plus 30 C. It is desirable to employ an inert reaction medium such as a lower alkanol, an alkyl ether (e.g., ethyl ether), a cyclic ether (e.g., tetrahydrofuran), a halogenated aliphatic hydrocarbon (e.g., chloroform), 21 lower alkenone (e.g., acetone), or an aromatic solvent such as benzene.

A basic material is necessary to effect the addition of the mercaptans to the carbamate of dichloroformaldehyde oxime. Among the suitable basic materials are sodium hydroxide, potassium hydroxide, triethylamine, tributylamine, dimethylaniline, diethylene diamine and potassium t-butoxide.

The carbamate of dichloroformaldehyde oxime used as a starting material for the preparation of the compounds of Formulal of this invention are disclosed and claimed in copending application Ser. No. 640,330, filed May 22, 1967 (Case No. 21,892). These compounds are conveniently prepared by reacting one mole of phosgene oxime with a mole of a lower-alkyl isocyanate. The reaction is conducted in the presence of a solvent such as benzene and from 1 to 10% by weight of a basic catalyst such as triethylamine.

The compounds of Formula l have pesticidal activity and can be used as insecticides and soil nematocides in the protection of decorative foliage and agronomic crops from infestations of insects and ascarids such as the Southern Armyworm, Nasturtium Aphids, Two- Spotted Spider Mite, Confused Flour Beetle, Large Milkweed Bug, German Cockroach, and the Southern Corn rootworm. For use as an insecticide, nematocide or acaricide the compounds of Formula I are incorporated in an effective amount (generally between about 0.1 and 95.0% by weight of the composition) into an active formulation containing a conventionally useful diluent. The diluent may be chosen so as to give of formulation and the concentration of active components.

The following examples are presented to further illustrate the present invention.

EXAMPLE A Preparation of O-Methylcarbamoyl Dichloroformaldehyde Oxime o p li f f f 1? To a stirred mixture of 48.5 parts of distilled phosgene oxime and 28.4 parts (by volume) of methyl isocyanate in 150 parts (by volume) of benzene is slowly added ca. parts (by volume) of triethylamine until further addition produces no noticeable exotherm. After 2 hours, an additional 20 parts (by volume) of methyl isocyanate is added and the mixture is allowed to stand overnight.

The resultant mixture is concentrated in vacuo and partitioned between 200 parts (by volume) of ether and 25 parts of water. The ether layer is washed with dilute hydrochloric acid, saturated sodium chloride, dried over magnesium sulfate, treated with activated charcoal, and concentrated in vacuo to yield 55.1 grams (76% based on phosgene oxime) of orange oil which crystallizes on seeding and cooling; melting point ca. 25 C. This material, combined with another 19.7 grams of crude product of similar quality in. 200 milliliters of ether, is washed with 20 parts (by volume) of 5% potassium hydroxide solution (dark wash) and washing is completed as before. The dry ether solution is brought to the cloud point with 150 milliliters of petroleum ether, cooled to 0 C. and seeded. Further slow cooling to 55 C. yields light yellow crystals which are collected and washed with petroleum ether; 55.1 grams, melting point 3 l.5-32.5 C.

Purification of O-methylcarbamoyl dichloroformaldehyde oxime is also achieved by passing crude product through a film molecular still at 4075/0.005 mm. Hg. Under these conditions, phosgene oxime carbamate collects as a colorless solid on the condenser and is removed by subsequent replacement of cold with hot water. Unreacted phosgene oxime collects in the Dry Ice traps. A sample of this material crystallized from 1:1 ether petroleum ether as fine white crystals, melting point 32.833.6 C.

EXAMPLE B Preparation of O-Ethylcarbamoyl Dichloroformaldehyde Oxime Employing the procedure of Example A, a mixture of equirnolar amounts of distilled phosgene oxime and ethyl isocyanate in benzene is treated with triethylamine until no further exotherm is observed with the addition of small amounts of the triethylamine. After standing, excess ethyl isocyanate is added to the reaction mixture and the mixture is permitted to stand at room temperature for several hours. The mixture is then concentrated under reduced pressure, partitioned between ether and water, the ether layer is separated from the water and washed with hydrochloric acid followed by saturated sodium chloride, then dried and concentrated under vacuum. O-ethylcarbamoyl dichloroformaldehyde oxime is recovered in good yield.

In similar fashion, O-isopropylcarbamoyl dichlorofomialdehyde oxime is prepared employing the above procedure, but substituting isopropyl isocyanate for methyl isocyanate.

EXAMPLE 1 Preparation of O-(Methylcarbamoyl) ethylthiochloroformaldehyde Oxime A mixture of 1.86 parts of ethanethiol and 3.37 parts of potassium t-butoxide in 25 parts of methanol was added slowly to 5.13 parts of phosgene oxime methylcarbamate in 25 parts of methanol maintained at 15 C. by a cooling bath. After addition is complete, the mixture was allowed to come to room temperature. The methanol was removed under vacuum and the residue was partitioned between ml. of etherbenzene and water. The organic phase was washed successively with dilute potassium hydroxide and saturated salt solution. After filtering through magnesium sulfate, the mixture was concentrated in vacuo to give 4.54 parts of oil which crystallized on cooling. Recrystallization from either-hexane gave 3.15 parts (53%) of colorless crystals, M.P. 37.0-38.0 C. A sample recrystallized again for analysis melted at 37.538.5 C.

EXAMPLE 2 Preparation of O-(Methylcarbarnoyl) methylthiochloroformaldehyde oxime In a tared mixture of 17.5 g. (0.102 mole) of phosgene oxime methylcarbamate in 100 ml. of benzene was collected 6.2 g. (0.139 mole) of methyl '70 C. and vacuum sublimed at 5560 C./0.2 mm. to

give colorless crystals, melting point 63.2-64.8 C.

EXAMPLE 3 Preparation of O-(Methylcarbamoyl) benzylthiochloroformaldehyde oxime vol 0 The reaction was carried out in the same manner as Example 1 replacing ethyl mercaptan with benzyl mercaptan. The crude product was recrystallized from toluene and from a toluene-hexane mixture at C. to give a 61% yield of colorless plates, m.p. vl03.0-1 05.0 C.

EXAMPLE 4 Preparation of O-(Methylcarbamoyl) phenylthiochloroformaldehyde oxime The reaction was carried out as in Example 1 replacing ethyl mercaptan with thiophenol. The crude product wasrecrystalli'zed twice from toluene to give a 75% yield of slightly yellow crystals, m.p. l25.0-l27.0 C.

EXAMPLE 5 Preparation of O-(Methylcarbamoyl) allylthiochloroformaldehyde oxime Cl 0 ll The reaction was carried out in the same manner as Example 1 except that n-propyl mercaptan replaced ethyl mercaptan and the reaction was run at -35 C. instead of l5" C. The crude product was recrystallized twice from ether-hexane at -55 C. to give a 69% yield of colorless needles, m.p. 38.540.0 C.

EXAMPLE 6 Preparation of O-(Methylcarbamoyl) a]lylthiochloroformaldehyde oxime l l NHCH3 The reaction was carried out in the same manner as Example 1 except that allyl mercaptan replaced ethyl mercaptan and the reaction was run at 35 C. instead of -1 5 C. The crude product was purified by chromatog- 5 raphy on silica gel using 5% methanol in benzene as the eluting solvent. The crystalline fractions were recrystallized from ether-hexane at -5 5 C. to give colorless crystals, m.p. 46.0-48.5 C.

EXAMPLE 7 Preparation of O-(Methylcarbamoyl) tbutylthiochlorofon'naldehyde oxime The reaction was carried out in the same manner as Example 1 replacing ethyl mercaptan with t-butyl mercaptan and with the reaction temperature at C. instead of -l5 C. The crude oily product could not be completely freed of an impurity, but infrared and nuclear magnetic resonance spectra attested to the presence of a larger percentage of the desired compound.

EXAMPLE 8 Preparation of O-(Methylcarbamoyl) bismethylthioformaldehyde oxime About 75 ml. of methyl mercaptan was collected in a 3-neck flask containing 10.0 g. (0.059 mole) of phosgene oxime metbylcarbamate. The flask was equipped with a Dry-Ice-acetone condenser and cooled with an alcohol bath at --20 C. With the system under nitrogen, 13.2 g. (0.12 mole) of potassium t-butoxide was added in small increments over about 20 minutes. The viscous mixture was stirred an additional 30 minutes after removing the cooling bath. The infrared spectrum indicated reaction was complete. After adding 50 ml. of benzene, the mixture stood open overnight. Additional benzene was added and the mixture was water-washed and dried and left in a beaker. Evaporation of solvent, seeding and further drying of the residue in a vacuum dessicator gave mostly crystalline solids. Recrystallization from ether gave 8.9 g. (78%) of colorless crystals, m.p. 57.4-58.4 C. and 57.0-58.2 C. as two crops.

EXAMPLE 9 Preparation of O-( Methylcarbarnoyl)bisethylthioformaldehyde oxime .&E?%9i ,,-,9: :?l i9 The reaction was carried out in the same manner as in Example 8 replacing methyl mercaptan with ethyl mercaptan. The crude product was recrystallized from ether to give colorless crystals, m.p. 67.5-67.8 C.

EXAMPLE Preparation of (O-Methylcarbamoyloxime) (benzylthio)methylthio formaldehyde oxime A mixture of 12.4 g. of benzyl mercaptan and 5.4 g. of sodium methoxide in 100 ml. of methanol was added dropwise over a minute period to a stirred mixture of 1 8.3 g. of O-(methylcarbamoyl) methylthiochloroforrnaldehyde oxime as prepared in Example 2 in 50 ml. of methanol cooled to 10 C. After 30 minutes, the mixture was allowed to come to room temperature and was worked-up as described in Example 1. The product was isolated as a solid showing strong infrared absorption at 1,500, 1,710, and 3,400 cm typical of the oximecarbamate function.

EXAMPLE 1 1 Insecticidal and Acaricidal Activity The compounds of this invention are tested for activity against common pests by the following procedures.

1. Southern Armyworm (Prodenia eridania Cram.)

Compounds to be tested are made up as 0.1% solutions as above. Sieva lima bean leaves are dipped in the test solution and set in the hood to dry. When dry, they are placed in four-inch petri dishes which have a moist filter paper in the bottom, and ten third-instar armyworm larvae about three-eighths-inch long are added to each dish. The dishes are covered and held at 80 C., 60% RH. After 2 days, mortality counts and estimates of the amount of feeding are made.

2. Nasturtium Aphids (Aphis rumieis L.)

The compounds to be tested are made up as 0.1% 0.01%, and 0.001% solutions in 65% acetone-35% water. Three inch pots containing a nasturtium plant 2 inches tall and infested 2 days before are selected for testing. The pots are placed on a turntable (4 RPM) and sprayed for two revolutions with a No. 15 DeVilbiss Atomizer at psi air pressure. The spray tip is held about 6 inches from the plants and the spray is directed so as to give complete coverage of the aphids and the plants. The sprayed plants are laid on their side on white enamel trays (Wk-inches X IPA-inches X inches) which have had the edges coated with No. 50 S.A.E. oil as a barrier. Mortality estimates are made after holding for 2 days at 70 F., 50% RH.

3. Two-spotted Spider Mite (Tetranychus telarius I.)

Compounds to be tested are made up as 0.1% solutions in acetone-35% water. Sieva lima bean plants with the first pair of leaves 3 to 4 inches in size are infested about five hours before testing, using about 100 to 200 adult mites per leaf. The infested leaves are dipped in the test solutions (in 4-inch crystallizing dishes) for 3 seconds, and the plants set in the hood to dry. The treated plants are held for 2 days at F., 60% R.H., and the adult mite mortality calculated by counting dead and alive adults on one leaf under the 10X binocularscope. The other leaf is held an additional 5 days and then is examined at 10X power to estimate the kill of eggs and newly-hatched nymphs, giving a measure of ovocidal and residual active, respectively.

4. Confused Flour Beetle (Tribolium confusum Duv.)

Compounds to be tested are made up as 1.0% dusts by mixing 0.1 gm. of compound with 9.9 gm. of Pyrax ABB talc, wetting with 5 ml. of acetone and grinding in a mortar and pestle until dry. 125 mg. of this 1% dust is then blown into the top of a dust settling tower with a short blast of air at 20 psi. The dust is allowed to settle on 4-inch petri dishes for 2 minutes. The dishes are removed and 25 adult confused flour beetles are added immediately. The dishes are held for 3 days at 80 F., 60% R.H., following which mortality counts are made. 5. Large Milkweed Bug (Oncopeltusfasciatus Dall.)

The 1% dusts described in the Confused Flour Beetle test are also used in this test. 25 mg. of the 1% dust is sprinkled evenly over the bottom of a 7-inch crystallizing dish using a screen-bottom plastic cup about fiveeighths inch in diameter as an applicator. Twenty adult bugs are added and a screen cover put on the dish. Water is supplied in 2 ounce bottles with a cotton wick. Mortality counts are made after holding for three days at 80 F., 60% R11.

6. German Cockroach (Blattella germanica L.)

The procedure is the same as for the large Milkweed Bug; however, only adult males are used in this test.

7. Southern corn rootworm Diabrotica undecimpunctata howardi Barber The compound is formulated as a dust and incorporated into the soil at the equivalent of 10 and 50 pounds per 6-inch acre. The soil is sub-sampled into one-ounce wide mouth bottles, and 10 6- to 8-day old rootworm larvae added to each bottle, which is then capped. Mortality counts are made after 6 days at 80 F 60% RH.

Test results are summarized in Table I (reported as mortality).

TABLE I.PERCENT MORTALITY Rootworm Army Aphids Spider Flour Milkweed German worms mite beetle b1}; cockroach Lb. Lb. Compound .1% 1% -01% 001% 0 1% 10 1% 50 acre 10 acre CHQS O 100 100 100 100 37 100 100 100 ll C=NOC-NHCH:

CHeS O 100 100 100 90 0 100 100 75 100 60 CHQS TABLE I.PERCENT MORTALITY Rootworm Army Aphids Spider Flour Milkweed Gormnnworms mlto beetle but: cockroach Lb. Lb. Compound .1% .1% .01% .001% .01% 1% 1% 1% 601mm 10 acre OzHsS\ fl) I 80 100 100 100 100 100 90 100 25 C=N O-CNHCH; r Cl CHHES\ E 0 100 100 50 95 0 100 0 45 0 /C=NO -NHCH l ss nCaH S W 60 100 100 20 81 100 100 85 45 C=NO-C-NHCHs CHg=CH-CH2-S\ a) 60 100 100 90 O 92 100 /C=N-OCNHGHQ o1 0 100 100 90 0 0 0 0 0 C z-S H C=NOCNHCHa C=NO- NHCH3 C1 ll-C4H9S O 100 100 EXAMPLE 12 tzttztittaetoat st am 2:0 seat i3? Nematocida] i i troduced into the soil. One week after treatment, the

soil is planted to a root-knot nematode susceptible to- To demonstrate the nematocidal activity of several mato plant. After a months growing time the tomato representative oxime carbamates against the root-knot plants are removed from the soil. The roots are washed nematode, test compounds are mixed with a po ing and examined for nematode injury. The plants are soil containing root-knot nematodes (Meloidogyne sp.) rated according to the following scale:

eggs and larvae. One quart of soil is placed in a l-gallon 0 Complete control stainless steel beaker. Predetermined amounts of the l High degree of control appropriate formulated oxime carbamate is pipetted 2 No control onto the soil which is then thoroughly mixed on a Rates of application of the toxicants are at 50, 10 or 5 mechanical mixer. The treated soil is then distributed lbs/acre. The results obtained are reported in Table 2.

TABLE II Root-knot nematode control lb./A. 10 lbJA. 5 lbJA.

m E2 We claim: ing of methylthio, ethylthio and benzylthio; and R is l. A compound of the formula: lower-alkyl.

2. The compound according to claim I: O-(methylw carbamoyl)bis-methylthioformaldehyde oxime.

\ 5 3. The compound according to claim 1: O-(methylcarbamoyl)bis-ethylthioformaldehyde oxime.

4. The compound according to claim 1: O-(methylcarbamoyl )bis-benzylthioformaldehyde oxime. wherein R and R are selected from the group consistm m 9 

2. The compound according to claim 1: O-(methylcarbamoyl)bis-methylthioformaldehyde oxime.
 3. The compound according to claim 1: O-(methylcarbamoyl)bis-ethylthioformaldehyde oxime.
 4. The compound according to claim 1: O-(methylcarbamoyl)bis-benzylthioformaldehyde oxime. 